Temperature-Dependent Kinetic Equation

for Catalytic Oxidation of Sulfur Dioxide

John 1. Harris’ and Joseph R. Norman2

School of Chemical Engineering, University of ITew South Wales, Sydney, Australia

Low-conversion and integral-conversion experiments were performed to investigate the rate of the catalytic
oxidation of sulfur dioxide using two commercial vanadium pentoxide catalysts at temperatures from 450-
580°C over a wide range of compositions. Temperature-dependent correlations were derived for each
catalyst based on a new form of kinetic expression. These correlations fitted the data almost as accurately
as the particular correlations derived for each temperature. A temperature-dependent relationship was also
derived using the proposed kinetic expression for the poisoned catalyst data published by lshii (1 966).

T h e recent developments in optimization and direct digital
control of industrial operations cannot be applied t o full
effect unless the traditional areas of chemical engineering
have received sufficient attention to produce accurate mathe-
matical descriptions. To derive such equations the funda-
mental mathematical model must incorporate all the signifi-
cant variables in an adequate flexible form, and the param-
eters in the model must be accurately determined to best fit
experimental data. One area where a n accurate correlation has
not been developed, even though many authors have tried, is
the rate of the catalytic oxidation of sulfur dioxide. Burkhardt
(1968) concluded that there was no single kinetic expression
available which was satisfactory over a wide range of composi-
tions and temperatures. More fundamentally, Livbjerg and
Villadsen (1972) surmized that probably no single rate ex-
pression can be applied in the whole range of industrial operat-
ing conditions. And such a kinetic expression is essential for
the optimization or direct digital control of the converter in
a sulfuric acid plant.
This paper discusses the inadequacies of previous correla-
tions, describes a series of experiments and presents correla-
tions of the data which applied over a wide range of tempera-
tures for the oxidation of sulfur dioxide, in the presence of
nitrogen, over two commercial vanadium pentoxide catalysts.
The stoichiometric equation for this reaction is
commercial vanadium
so2 + 11202
pentoxide catalyst
so0
Previous Kinetic Studies
The field of kinetic studies of the catalytic oxidation of
sulfur dioxide has been reviewed several times (Boreskov
et al., 1967; Davidson and Thodos, 1964; Duecker and West,
1959; Eklund, 1956; Livbjerg and Villadsen, 1972; Weychert
and Urbanek, 1969). However, a more detailed appraisal of
the attempts by previous investigators to develop temperature
dependent kinetic expressions is presented in this paper. A
summary of the more important previous studies is shown in
Table I.
1 Present address, Conzinc Riotinto of Australia Ltd., 95 Collins
St., Melbourne. To whom correspondence should be addressed.
2 Present address, J. R. Norman and Associates, Sydney,
Australia.
Kinetic Expressions. Throughout the literature the
kinetic expressions employed to correlate the experi-
mental data were frequently variations of one of t h e follow-
ing two expressions. One is t h e Hougen-Watson (1943,
1947) form of expression given by
in which
(3)
Equation 2 can be expressed alternatively as
The other commonly used expression is the power series
expression given by
r = APo~~Pso~CPSO~~F~, (5)
It is emphasized that KO,,Kso,, and Kso3in Equation 2 are
regarded solely as parameters in this study; any relationship
they bear to adsorption equilibrium constants has been
ignored. Even though Hougen-Watson kinetic expressions
were derived from an adsorption-based mechanistic approach,
hypothesizing a reaction mechanism from the fit of these
expressions to experimental data was shown by Weller (1956)
(1) to be fallacious. Furthermore, commercial vanadium pen-
toxide catalysts which incorporate potassium salts have been
shown (Boreskov et al., 1971; Frazer and Kirkpatrick, 1940;
Kiyoura, 1940; Mars and llaessen, 1964; Topsoe and h’ielsen,
1948) to involve a liquid catalyst supported by the porous
particle structure in the active temperature region of 400-
6OOOC. This has led Glueck and Kenny (1968) to study the
reaction rate for unsupported catalyst melts and Holroyd and
Kenny (1971) to study the rate of adsorption of sulfur dioxide
in vanadium pentoxidejpotassium pyrosulfate melts. Al-
though adsorption-based mechanisms are certainly incorrect
for commercial vanadium pentoxide catalysts, Hougen-
Watson kinetic expressions are still useful as empirical mathe-
matical models.
h limitation of the power series kinetic expression (Equa-
tion 5 ) is that i t does not apply a t the start of a reaction where
Pso3 is zero. Depending on whether the parameter D is

564 Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972
positive or negative so the initial rate of reaction is zero or
infinite. Correlations derived from this expression are there-
fore limited to conversions above a minimum value selected
by t,he investigator. AIars and van Krevelen (1954) overcame
this limitat,ioii by incorporating Psoa in a h e a r combination
with Pso2. Using their quasipower series expression, they
attempted to correlate experimental data from several
sources. However, the .?'Son term in the numerator required
a variable exponent in order to correlate Calderbank's (1952)
data.
Previous Temperature Relationships. Two of t h e earliest
temperature relationships (Krichevskaya, 1947; Calder-
bank, 1952, 1953) were based on power series kinetic
expressions. Similar procedures were employed in t h e two
derivations. -1 power series expression was assumed t o
correlate t h e dat'a a t t h e individual temperatures, and the
values of t h e reaction velocity constant were expressed
as -1rrhenius functions of temperature. However, Krich-
e v s k a p (1947) did not' show conclusively t h a t the power
series expression which applied a t 500°C, namely Equation 5
in which B = 0.5, C = 0.5, and D = -0.5, also applied a t
475" and 575°C. * i t each of these temperatures only two runs
were performed and the resultant values of k in the assumed
expression were averaged. Even at' 5OO"C, the values of k
varied b y more than 20%, and i t was possible that a n even
larger variation would have been observed a t the other two
temperatures.
Although the temperature relationship derived by Calder-
bank (1952, 1953) has been employed t o model sulfur dioxide
converters (Calderbank, 1953; Homme and Othmer, 1961),
its derivabion is not reliable. First, t'he values of the exponents
in Equation 5, stated as B = 0.8 and C = 0.4, with D set
equal t o zero, were derived by averaging 11-idely varying
values. At 370"C, the exponents were determined as B =
0.73 arid C = 0.35 while a t 410"C, the values of the exponents
were B = 0.85 and C = 0.56. Secondly, there were wide
variations bet'ween the values of k. in the proposed expression
which were determined for the runs in each set of data.
Third, adequate proof was not given to support the claim t h a t
the equilibrium fact'or,Feq, in the proposed equation accounts
for the effect of sulfur trioxide 011 the rate of reaction for
conversiom greater than 10%.
I n three other cases where the one power series expression
was used t o correlate data a t various temperatures, the values
of 12 did not follow Arrhenius temperature relationships
(Eklund, 1956; Ishii, 1966; Kadlec et al., 1970). I n fact, for
t h e two samples of the catalyst Ishii examined, the relation-
ships were almost parabolic and tended to exhibit maximum
values. However, as in Krichevskaya's (1947) and Calder-
bank's (1953) studies, the kinetic equations employed in
these three studies did not yield a satisfactory fit to the in-
dividual sets of data and hence the observations made re-
garding temperature relationships have only limited sig-
nificance.
The att'empts at' developing a temperature-dependent
relationship based on Hougen-Watson kinetic equations have
likewise involved poor correlations a t the individual tempera-
tures. I n the low conversion studies of Davidson and Thodos
(1964), the values determined for the parameters did not
minimize the chosen criterion of fit t o the data. This resulted
in the deviations of the calculated rates of reaction from the
experimental rates being a function of the partial pressure of
sulfur trioxide, Pso,. Thus it was by chance t h a t t h e estimated
values of the parameters were positive and followed the
Arrhenius relationships. l l a t h u r and Thodos (1966) chose
inadequate forms of expression for correlating the data a t the
individual temperatures. Although conversions as high as
9.82y0 were obtained, a sulfur trioxide term was not incor-
porated in t h e expressions. Boudart (1967) suggested t h a t
incorporating such a product term would enable a considerably
closer fit t o the data t o be achieved.
Both Kubota e t al. (1959) and Boreskov e t al. (1968) found
i t necessary to propose different temperature relationships
over separate limited temperature ranges. Kubota et al. (1959)
derived tivo temperature relationships which covered a dis-
continuous range of temperatures, up t o 450°C and above
500°C. I n applications of these expressions, Chartrand and
Crowe (1969) and Kubota e t al. (1961) interpolated rates of
reaction for temperatures between 450" and 500°C so t h a t
both the rates of reaction and their derivative with respect to
temperature were continuous functions of temperature.
Boreskov et al. (1968) employed the same kinetic expression
over the temperature range of 400-642OC but found t h a t
different temperature dependencies of the parameters applied
a t various temperature levels. The reaction velocity constant,
k , followed the Arrhenius expressions for temperatures from
400-440°C and from 440-560°C. Above 56OoC, k was con-
stant. However, these results were not satisfactorily proved
by the experimental program. The proposed kinetic equation
ivas fully tested only a t 485OC. It was shown t o apply at 522°C
over a wide range of conversions for one initial feed gas com-
position. At 462°C for the same initial feed gas composition,
it applied only for conversions above 70%. At all other tem-
peratures, the proposed kinetic equation was assumed to
apply and the value of k was determined from a single high
conversion run.
X a r s and hfaessen (1964) have shown that vanadium must
be present in the pentavalent state (V5+) to effect the oxida-
tion of sulfur dioxide and the V 4 + so formed is oxidized back
t o V5+ by t h e chemisorption of oxygen. Previously Tandy
(1956) had shown t h a t the fraction of the vanadium present
as V5' in a mixture of pure KzS04 and VnOs, when catalyzing
the oxidation of sulfur dioxide, remains constant from 600-
44OOC but decreases markedly for temperatures below 440°C.
Tandy (1956) suggested t h a t the break may occur a t a lower
temperature than 440°C for industrial catalysts. However,
this chemical change makes i t unlikely t h a t one kinetic
expression could apply from 400-600" C, but one expression
may be able t o be developed from 450-600°C.
Experimental
The aim of the experimental study was t o generate kinetic
data for two commercial vanadium pentoxide catalysts
(Types 11 and 210 Monsanto catalysts which were supplied
by Australian Fertilizers Ltd.) over the range of compositions
and temperatures encountered in industrial applications.
Since the data were to be used in the development of tempera-
ture-dependent kinetic expressions, it was desirable t o perform
series of runs a t designated temperatures under isothermal
plug-flow conditions. The establishment of a n isothermal
reaction zone was complicated by the large exothermic heat of
reaction. Previous investigators have employed some elabo-
rate reactor designs t o minimize the heating effects. The
equipment shown schematically in Figure 1 was used success-
fully in this study.
Apparatus. Separate supplies of sulfur dioxide, oxygen,
and nitrogen were employed to permit a wide range of
gas compositions t o be examined. Sulfur dioxide was ex-
tracted f r o m above a d r y liquid supply, and oxygen and
nitrogen were available as high-pressure gases with u p
Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972 565
 .A
5
c
0
fdi

2 E
3

0 0
Y U
0, 0,
U - D H H 8 1 1
U-D H t i HF H H H
m
1 .-Jc &
c
2
d
a

II /I II
b L b

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566 Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972
 Twin 0 . 6 KW H e a t e r s
wound II I S i l i r i Tub8

4 Insulation w i t h
8 i i c l i i c i l ha*t-less

uu u
o -.

Figure 1 . Schematic diagram of experimental equipment

to 25 ppm of water vapor content. The supply pressures

were stepped down with reducing valves and the oxygen
and nitrogen streams dried with molecular sieves. This
drying step was essential since both catalysts were per-
manently damaged by moisture. The gas pressures were
then adjusted to 880 mm Hg abs using needle valves, the gas
flow rates measured with rotameters, the gases mixed, and fed
to the reactor tube.
The reactor tube consisted of a 4-ft length of 12.5mm i.d.
silica tube. I n passing down this tube, the gas was alternately
heated, reacted under isothermal conditions, and finally
cooled. The heating zone was formed by twin O.&kW coils
wrapped around a 11/4-in. i.d. silica tube arranged concentri-
cally around the reactor tube. The heating coils were insulated
with vermiculite and connected to variable transformers.
The reaction zone was 4 in. long and was spanned by the
thermocouples by which the temperatures TI, TP,and T3were
measured. It was part of an insulated zone around which two
electrical heaters were wrapped. For a temperature 2'1 of
580°C and no reaction occurring, the heaters were required to
supply approximately 250 W in order to maintain the tem-
peratures Tzand T 3 a t 580°C for an average gas flow rate.
The experimental runs were confined to those gas compositions
and flow rates for which the heaters were required to supply
more than 150 W so that temperatures T Band T3were main-
tained equal to TI.Those compositions which did not permit
isothermal conditions to be established because they emitted
very high heats of reaction were beyond the range of in-
dustrial mixtures and hence little was lost by their omission.
To facilitate in the dissipation of the heat of reaction, the
catalyst samples were divided into small separate layers and
-
v
ri

d
W
-42
positioned over the length of the reaction zone.
The temperatures TI, T,, and TS were measured with
28-gage Chromel-hlumel thermocouples connected to a Kent
Mark I1 recorder which had a range of 300-600°C. The
system was accurate to +1.5"C when standardized against
solidifying zinc. The inlet and outlet pressures to the reactor

Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972 567
 Table 11. Ranges of Variables Studied in l o w Conversion Experiments
Monsanto Reaction Ranges of midconversion interfacial partial pressures, atm
catalyst type temp, ‘ C No. of runs so2 0 2 SO3 x 102
11 450 12 0.075-0.530 0.191-0.481 0.16-0.83
11 510 12 0.073-0.454 0.082-0,369 0.22-1.94
11 580 11 0.066-0.564 0.030-0.332 0.34-2.42
210 450 14 0.082-0,336 0.060-0.413 0.15-0.80
210 490 11 0.077-0.440 0.147-0.476 0.42-1.26
210 510 8 0.119-0.398 0.162- 0.538 0.35-1.21
210 550 13 0.071-0.460 0.091-0.369 0.22-1.37
210 580 9 0.144-0.568 0.114-0.381 0.54-2.10

Table 111. Ranges of Variables Studied in Integral Conversion Experiments

Monsanto Reaction Ranges of interfacial partial pressures, atm
catalyst type temp, ‘ C No. of runs SO2 0 2 so3
11 450 9 0.034-0.138 0.355-0.713 <0.063
-
11 510 9 0.021-0.129 0.159-0.733 <0.068
11 580 8 0.021-0.135 0.050-0.352 20.049
210 450 7 0.038-0.148 0.235-0.658 50.055
210 510 7 0.030-0.179 0,097-0,274 50.106
210 580 7 0.014-0.116 0.045-0.575 50.090

tube, P I and Pz,could be varied by operating a valve located
in the exit line from the reactor. The final piece of equipment
was a packed column in which water was used to absorb un-
reacted sulfur dioxide from the gas stream before i t was
vented to the atmosphere.
Procedure. V h e n a bample of catalyst was to be loaded
into the reaction zone, it was loaded in layers less t h a n ‘ / a
in. in height and separated by a t least 1 in. from each
other. Because it had been reported t h a t an initial period
of unsettled activity exists when starting up with a va-
nadium pentoxide catalyst (Baron et al., 1952; Goldman
e t al., 1957), a mixture of 10% SO2 in air was reacted
over the fresh catalyst a t 550OC for 30 h r before runs were
performed. The only point required t o be mentioned
concerning the procedure for each run was that the desired
reaction bed temperature was always approached by cooling
from a higher temperature which eliminated the effect of a
possible “reaction hysteresis” between the runs in a series.
The concentrations of sulfur dioxide in the inlet and outlet
reactor streams were determined iodometrically. A known
volume of standardized iodine solution was pipeted into a
500-ml Dreschel bottle, diluted to 400 ml with distilled water,
and starch indicator was added. The sample stream line was
purged with the gas to be analyzed, the Dreschel bottle was
connected, and the sample gas was dispersed through the
iodine solution a t a rate of approximately 75 ml/min until
the solution was decolorized. The gas which passed through
the Dreschel bottle was collected and its volume measured in
a graduated cylinder inverted over water. The volume of
iodine solution was chosen so t h a t about 600 ml of gas was
collected. The analyses were performed in duplicate and
repeated if they disagreed by more than 2% of the difference
between the volumes collected in the analyses of the inlet
and outlet streams. I n the integral conversion runs, where
there was a considerable difference between the sulfur dioxide
concentrations in the inlet and outlet streams, this figure was
usually less than 0.3%. And this represents the major analyti-
cal error, since tests showed t h a t all of the sulfur dioxide in a
sample stream reacted with the iodine.
The quantities measured in each experimental run included
the reactor diameter, D,, average size of the catalyst particles,
DP, weight of catalyst, We, reactor temperature, T,inlet and
outlet pressures, P1 and Pz, feed flow rates of sulfur dioxide,
oxygen, and nitrogen, FDo, F o o t and F N o , the volume and
concentration of the iodine solution used in the analyses of the
gas streams, V I and CI, the volumes of the gases collected
over water in the analyses of the inlet and outlet streams,
S V I and SV2, the temperature of the collected gases, S T ,
and the barometric pressure, BP. These data were then pro-
cessed as follows. The sulfur dioxide concentrations in the inlet
and outlet reactor streams were calculated from the iodometric
analyses and used in conjunction with the feed flow rates of
oxygen and nitrogen, FOo and FNo, t’o determine the feed
flow rate of sulfur dioxide, FDo, and the overall conversion,
X p The consistency of each experimental run was checked
by comparing the calculated value of PDo with the experi-
mentally measured value. I n the low conversion (conversions
limited t o less than 10yo)runs which were performed, i t was
assumed that the average conditions in the reactor (average
rate of reaction and the midconversion interfacial partial
pressures) were sufficient to characterize each run. The ex-
ternal film diffusion pressure and temperature differentials
required to calculate the interfacial conditions were deter-
mined by a method which has been used previously for the
SOZ, 02, SOI, and Nz systems (Hougen and Watson, 1947;
Olsonet al., 1950; Smith, 1956).
Experimental Results. X total of 147 experimental
runs were performed, comprized of 10 runs t o determine
the region where pore diffusion was absent, 90 low con-
version runs, and 47 integral conversion runs. The number
of runs performed and t h e ranges of the partial pressures
investigated a t each temperature are shown from t h e low
conversion runs in Table I1 and t h e integral conversion
runs in Table 111. The preliminary pore diffusion experi-
ments showed t h a t these runs were conducted in a particle
size, temperature-, and reaction-rate region where pore
diffusion was absent. A sample set of the low conversion
experimental results is shown in Table IV for the Type 11
catalyst a t 450°C and a sample set of the integral conversion
experimental results is shown in Table V for the Type 11
catalyst a t 450°C. A complete set of the experimental results
is contained elsewhere (Harris, 1971).

568 Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972
 Table IV. l o w Conversion Experimental Results for Type II Catalyst at 450°C
Run no. FDoa Xf x 102 G A P x ~ 103~ ~ PO* p802 p503 x lo2 r

L79 1.438 7.96 504 0.29 0.299 0.174 0.75 0.0865

L80' 1.960 6.99 572 0.34 0.308 0.219 0.83 0.1036
L81 2.479 5.55 617 0.33 0.290 0.271 0.81 0.1039
L82 2.443 6.20 67 5 0.35 0.393 0,239 0.80 0.1145
L83 3,086 4.12 659 0.31 0.348 0.338 0.75 0,0962
L84 3.115 3.33 630 0.26 0.373 0.367 0.65 0.0783
L85 0.842 8.59 433 0.19 0.286 0.111 0.52 0,0546
L86 0.776 5.60 374 0.12 0.191 0.119 0.36 0.0328
L87 0,772 4.03 462 0.07 0.225 0.095 0.20 0.0235
L88 0.745 3.90 554 0.06 0.267 0.075 0.16 0.0220
L89 2.655 2.71 419 0.24 0.272 0.530 0.75 0.0543
L90 3.607 3.84 713 0.33 0.481 0.384 0.79 0.1048
a Calculated value of FDo.

For example, for the data for the Type 11 catalyst a t 450°C
Table V. Integral Conversion Experimental Results (Table IV), t h e parameters in Equation 4 lvere determined as
for Type 1 1 Catalyst at 450°C A = 1.290, B = -0.02, C = 2.96, and D = -104. Also,
Run no. FDoa FOo FNo p1 pz x/ large positive values were obtained in the correlations derived
R22 0.948 3.06 4.28 850 802 0.225 from Equation 7 . These unexpected results did not indicate
R23 1.199 4.60 4.05 860 800 0.215 that the rate of reaction was iiicreased by increasing the par-
R24 1.026 4.75 2.69 846 796 0.252 tial pressure of sulfur trioxide. They were a consequence of the
R25 0.662 4.54 2.57 839 795 0.315 experimental conditions in which the weight of catalyst was
R26 0.635 2.40 1.99 828 800 0.371 fixed, the superficial gas velocities were of a similar order of
R27 0.364 2.03 1.62 828 808 0.526 magnitude for the runs in each series, and the conversions of
R28 0.325 1.30 1.53 813 803 0.566
3.20 1.38 833 803 0.536 sulfur dioxide were limited to less than 10%. The high mid-
R29 0.339
R30 0.534 2.55 4.28 835 793 0.259 conversion partial pressures of sulfur trioxide thus generally
corresponded to the high rates of reaction.
Heactor diameter, D , = 12.5 mm. Average catalyst particle
size = 0.40 mm. Weight of catalyst, W e = 3.336 grams. Correlations Derived for Published Low Conversion
a Calculated value of FDa. Data. Large negative values for t h e parameter D in
Equation 4 were also derived o n correlating t h e low c o n
version d a t a published by Davidson and Thodos (1964)
a n d N a t h u r and Thodos (1966). The parameters were
Low Conversion Correlations
determined a. A = 0.910, B = 3.62, C = 5.69, a n d
Several kinetic expressions were tested for correlating the D = -215 for t h e Davidsoii and Thodos d a t a a t 643°F.
low conversion data. The parameters in the expressions were For this correlation, 2, = 0.52 X l o w 6 (8, = 55.61 X
evaluated PO that the objective function, Z,, defined as which compares favorably with 2, = 23.70 X pertaining
t o the correlation proposed by Davidson and Thodos. The
mean absolute deviation, Cr,was likewise reduced from 12.9 to
was minimized. The nonlinear est,imationtechnique, statistical with the new correlation. An F-statistic test showed t h a t
ES'OP (Xormari and Souter, 1967), was applied t o determine it mas 99.95y0 certain t h a t the new correlation related to the
the minima. Various starting points, namely different iiiitial data, whereas this factor was only 48y0 for the correlation
values of the parameters in the kinetic equation, Ivere tested proposed by Davidson and Thodos. Improvements were also
in each case t'o ensure that the derived optimum was the global achieved in the fit to Davidson and Thodos data at 672' and
optimum. 722°F.
Three kinetic expressions, namely Equation 4, the ACD The parameters in Equation 4 for the three series B experi-
variant of Equation 4 ( B set equal to zero) and the quasi- ments conducted by N a t h u r and Thodos (1966) were deter-
power series espression given by mined as A = 0.820, B = 6.27, C = 0.81, D = -156 a t
649'F, A = 0.469, B = 5.90, C = 0.93, D = -122 at 701°F,
r = +
.JPo,~Pso,C(~PsoJDFeq (7) and A = 0.750, B = 4.76, C = 0.94, D = -90 a t 752'F.
satisfactorily correlated the eight sets of low conversion data Large negative values of the parameter D were observed once
as shown in Table VI. The confidence levels of the derived again. V i t h these correlations the values of 2, were lower by
correlations exceeded 99.9% in all inst'ances. The form of factors of 49, 10, and 5 a t 649, 701, and 752'F, respectively,
Equation 6 was arbitrarily derived as one which is not limited than the values pertaining t o the correlations proposed by
to conversions above a certain minimum value and incor- X a t h u r and Thodos. The mean absolute deviations, LT7, were
porat'es a rate constant and three exponents. reduced from 14.4 t o 2.0% a t 649"F, from 29.6 t o 6.9% a t
While t h e oxygen term B.Po,~/' in the denominator of 701"F, and from 3.9 to 2.3% a t 752OF. Although Equation 4
Equation 4 was not essential for correlating the data, the has more parameters than the expressions employed by
sulfur trioxide term was most necessary. And a n unusual Mathur and Thodos, they were justified by the improvement
aspect' of the correlations derived from Equation 4 and its achieved in the fit to the data. Whereas the confidence levels
.\CD variant was the large negat,ive values obtained for D. of their expressions were 91.8, 78.0, and 99.95% a t 649, 701,

Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972 569
 Table VI. Fit Achieved by Correlations of l o w Conversion Rate Data
Sum-of-squares, Obiectiva function, ZIX 10' Mean abs dev, U,
Catalyst type Temp, OC sa x 104 ACD-Eq 4 Eq 4 Eq 7 ACD-Eq 4 Eq 4 Eq 7
11 450 127.3 3.3 3.3 6.2 5.5 5.2 8.6
11 510 215.5 6.5 5.6 17.1 8.1 6.4 14.2
11 580 393.5 7.5 3.6 6.3 8.8 7.2 7.9
210 450 6.65 0.26 0.12 0.097 8.0 6.9 5.4
210 490 28.1 0.66 0.66 0.57 5.2 5.2 5.0
210 510 78.4 1.06 0.35 1.78 6.1 3.3 7.6
210 550 379.1 17.5 7.2 13.6 9.5 7.8 10.0
210 580 416.4 9.2 7.3 6.5 6.2 5.3 6.6

well suited for describing this pattern of behavior because

the numerator, even excluding F,,, decreases a t a rate exceed-
ing the direct proportionality with conversion. This over-
reacted decrease is counteracted by a decrease in t h e denomi-
nator term via negative values for the sulfur trioxide term,
DsPso,. It was proposed that a more appropriate Hougen-
Watson kinetic equation would incorporate a nearly constant
numerator and a denominator which increases with con-
version, as shown in Figure 2. This led to the proposal of
Equation 10 as well as the power series expression, Equation
11, which involves the same independent variables.

r= P s o ~ . $ o ~ Feq
,~~'~
o 0.5
Convsrsion, X
1.0
(A + B'Po2,0''2 $- c'pS02,0 f o'pso3)2
(10)

Figure 2. Variation with conversion of terms in Equations 4 r = APo~,~~PsoP,OC

and 10
and 752"F, respectively, the corresponding values with the
new correlations were 99.95, 95.5, and 99.95%.
Integral Conversion Correlations
Based on the correlation studies of the low conversion rate
data, four kinetic expressions were initially tested for fitting
the integral conversion data. The expressions chosen were
Equations 4 and 7 and their XCD variants, where the parame-
ter B was set a t 0.5 in the ACD variant of Equation 7. The
parameters were evaluated using the statistical EVOP tech-
nique so as t o minimize the objective function, &, defined as
in which W , is given by the catalytic reactor design equation:
(1 f P80a)DFeq (11)
The independent variables in these two equations are Pso,,,
and PO,,,,which vary only with the total pressure in the course
of a reaction, and Psoa.The equilibrium factor, Fe,, appearing
in Equations 10 and 11 is the same factor which is defined in
Equation 3. It can be written in terms of the new independent
variables by employing the relationships between them and
PSO,and PO,. However, the resulting expression is not pre-
sented here because Feq is more conveniently calculated from
Equation 3. It is noted that Equations 10 and 11 are almost
equivalent to Equations 4 and 7, respectively, for correlating
low conversion data.
The parameters in Equations 10 and 11 and the ACD
variants of these equations were determined t o fit each of the
six sets of integral conversion data. The four correlations thus
derived for each set of data yielded a n even closer fit t o the
data than did the correlations derived from Equations 4 and
7. The values of Zw achieved with the correlations derived
from the ACD variant of Equation 10 were 1.6% at 450"C,

W, = FDo s,"' (9)

All six sets of data were fitted closely by each of the four
expressions. For example, the ACD variant of Equation 4
yielded values of Zw of 2.6, 2.1, and 2.5% when fitted t o the
data for the Type 11 catalyst a t 450, 510, and 580"C, re-
spectively. Slightly better results were achieved using the
other three equations. I n the correlations derived from Equa-
tion 4, the values of the parameter B varied only slightly from
zero, and negative values were obtained for the parameter D.
The parameter B in Equation 7 assumed values close t o 0.5,
and positive values were obtained for D. The parameter values
did not follow any well-defined relationship with temperature.
The rate profiles calculated from the above correlations
showed t h a t the rate of reaction decreased only slowly for
conversions not approaching equilibrium. Equation 4 is not
2.0y0a t 51OoC, and 1.0% a t 580°C for the Type 11 catalyst,
and 1.3% a t 450"C, 1.5% a t 51OoC, and 1.2% at 580°C for
the Type 210 catalyst. Only minor reductions from these
values of Zw were achieved when the parameter B was varied.
Although Equation 11 gave almost identical results t o those
achieved with Equation 10, only the values of the parameters
in the ACD variant of Equation 10 followed Arrhenius tem-
perature relationships, as shown in Figure 3 for the Type 11
catalyst and in Figure 4 for the Type 210 catalyst.
Temperature-Dependent Correlations
Lines of best fit were drawn for A , C, and D in Figures 3 and
4. These lines were then used t o supply initial estimates of the
coefficients in Arrhenius expressions for A , C, and D, and a
statistical EVOP technique was employed to determine the
values of the coefficients which minimized Zw for the com-
bined runs on each catalyst. As no improvernerlts were

570 Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1 9 7 2

 0
0
.E
0
U
4

c
0 6

1°----I--'-. 0

0.1
1.15 1.20 1.25 1.30 1.35 1.40

+ lo3, OK-'
Figure 5. Comparison of correlations in fitting Ishii's (1 966)
integral conversion data for the poisoned catalyst at
Figure 3. Temperature dependency of parameters in ACD 500°C
variant of Equation 10 for Type 11 catalyst 0 Experimental data
0 Parameter A, A Parameter C, Parameter D - Correlation derived from Equation 14
_-. Correlation derived by lshii

IO
I

t 0.1
1.10 1.20 1.30 1.40
1.0

+ 12 , "i'
I

I15 120 1.25 130 135 110

Figure 6. Temperature dependency of parameters in
Equation 14 for poisoned catalyst examined b y lshii
L lo3, o f 1
(1 966)
0 Parameter A, U Parameter D
Figure 4. Temperature dependency of parameters in ACD
variant of Equation 10 for Type 210 catalyst
0 Parameter A, A Parameter C, C Parameter D The fit achieved to each of the six sets of data with the
temperature-dependent correlations was only slightly less
accurate than the fit achieved with the individual correlations.
achieved beyond the initial estimates, the graphically in-
For the Type 11 catalyst, the values of ZW were 1.6% (1.6%
dicated Arrhenius relationships represented the best correla-
for the correlation derived from the ACD variant of Equation
tions:
10) a t 45OoC, 2.3Q/, (2.0y0) a t 51OoC, 1.2% (1.0%) a t 58OoC,
Type 11 LIonsanto catalyst:
and 1.87, (1.5y0) for the combined sets of data. For the Type
A = exp (-5.69 + 4060/T) 210 catalyst, the values were 1.4Y0 (1.37,) a t 450"C, 1.7%
C = exp (6.45 - 4610/T) (1.5%) a t 510°C, 1.3% (1.2%) a t 580°C, and 1.5% (1.3%)
for the three sets of data.
D = exp (-8.59 + 7020/T) (12)
Correlations Derived for Published Integral Conversion Data
Type 210 Llonsanto catalyst:
Since Ishii (1966) used a constant feed composition in each
A = exp (-6.80 + 4960/T) run, Pso,,, and Pop,aare constant and Equation 10 simplifies
C = exp (10.32 - 735O/T) to the two-parameter expression given by
D = exp (-7,58 + 6370/T) r = Feq/(A + D.PsoJ2 (14)

Ind. Eng. Chem. Process Des. Develop., Vol. 1 1, No. 4, 1972 571
 This equation was shown to fit the nine sets of data which
contained sufficient runs for correlations to be derived more
closely than did the equation proposed by Ishii. This is il-
lustrated in Figure 5 for the poisoned catalyst a t 500°C.
Furthermore, as shown in Figure 6, the values of the param-
eters A and D in Equation 14 determined for the sets of data
for the poisoned catalyst followed Arrhenius relationships
given by
d = exp (-4.416 + 2815/T)
D = exp (-2 848 + 3929/T)
These relationships were shown t o yield the lowest value of
Zw of 9.6% for Arrhenius relationships. Furthermore, as
observed with the temperature relationships for the Types
11 and 210 Monsanto catalysts, these relationships resulted
in only a small loss of accuracy in the fit t o the data compared
to the individual correlations. The values of Zw were 15.8%
(15.3% for the individual correlation) a t 45OoC, 6.0% (5.5%)
a t 500°C, 9.4% (9.0%) a t 550"C, 5.9% (5.6%) a t 600"C, and
9.6% (9.2%) far the combined four sets of data.
Correlations Derived for Published Differential Conversion
Data at Various Preconversions
The only series of runs performed by Eklund (1956) in
which the concentrations of sulfur dioxide, oxygen, and sulfur
trioxide were all varied was a t 476°C. Hence this was the only
data which fully tested the kinetic expression he proposed and,
in particular, the unity exponent of Po,. For comparison, a
correlation of this data was derived from Equation 4. The
values of the parameters in this equation were determined as
A = 32.9, B = -41.4, C = 238, and D = 207 and the cor-
responding value of the objective criterion, Z,, was 0.27 X
10-l2 (8,= 56.4 X g-mo12/sec2g2). This represented a
considerable improvement in the fit to the data in comparison
to the correlation derived by Eklund for which 2, = 5.58 X
lo-'*. With the new correlation, the mean absolute deviation,
L-,, was reduced from 12.4 to 2.2% and the confidence level
of the correlation was increased from 96.5 to 99.95%.
I n the series of runs conducted by Eklund (1956) a t 525"C,
the eight gas compositions studied were formed by partially
converting four gases. These data were thus suitable for
independently testing the potential of Equation 10 as a kinetic
expression for the catalytic oxidation of sulfur dioxide. Since
the initial partial pressure of oxygen, PO,,^, was almost con-
stant for the four gases, the parameter B in Equation 10 was
set t o zero. The values of the other parameters were deter-
mined as A = 20.3, C = 40.5, and D = 515. This derived
correlation yielded a closer fit to the data than did the correla-
tion proposed by Eklund. The objective function, Z,, was
reduced from 4.07 X t o 0.30 X (Sa = 35.58 X
the mean absolute deviation, C,, was reduced from
5.4 to 1.S%, and the confidence level of the correlations was
increased from 99.5 to 99.9570.
Accurate correlations were also derived from Equation 4 for
the five sets of data obtained by Kadlec et al. (1970) for tem-
peratures between 400" and 480°C. The set of data a t 380°C
was not considered as it contained a doubtful value. Since the
data was obtained for gases formed by preconverting a gas
of constant composition, the concentrations of sulfur dioxide
and oxygen were linearly related to the concentration of sulfur
trioxide. Thus, Equation 4 simplifies t o
Significantly lower values of the objective function, Z,, were
obtained with the correlations derived from Equation 16
572 Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972
than with the correlations proposed by Kadlec et al. (1970).
The mean absolute deviation, C,, was reduced from 11.3% (k
= 0.48 in the expression proposed by Kadlec e t al.) to 5.2%
(A = 1.170, D = 10.3 in Equation 16) a t 400"C, from 7.3%
(k = 1.01) to 2.7% (A = 0.834, D = 3.47) a t 420"C, from
10.2% ( k = 1.78) to 3.3% ( A = 0.585, D = 3.00) a t 44OoC,
from 6.9% (k = 2.96) to 2.8% (A = 0.456, D = 1.78) a t
460°C and from 7.6ojO (k = 4.40) to 5.370 ( A = 0.340,
D = 1.75) a t 480°C.
(15) Conclusions
Temperature-dependent correlations were derived for the
integral conversion data for the Types 11 and 210 Monsanto
catalysts and the poisoned catalyst studied by Ishii (1966) by
expressing the parameters in Equation 10 as Arrhenius tem-
perature relationships. These correlations fitted the data
almost as accurately as the particular correlations derived to
fit the data a t each temperature. I n this respect the correla-
tions are unique, and the following points are made concerning
the general applicability of the method of deriving these
equations and the failure of t h e tested power series expression
to exhibit a temperature relationship.
It is regarded as important to the derivation of the tem-
perature relationships that the kinetic expressions were
initially examined with respect to the fit they yielded t o the
data a t the individual temperatures. This enabled a kinetic
expression t o be selected which closely fitted the data and one
in which the parameters followed Arrhenius relationships. It
is considered that the direct evaluation of a temperature
relationship, as reported in the literature for other reactions,
would have been much more difficult than the adopted pro-
cedure. For example, it could not have been expected that the
negative slopes of the parameter C in Figures 3 and 4 would
have been anticipated without examining the correlations a t
the individual temperatures.
The temperature relationships derived for the Types 11 and
210 Monsanto catalysts were based on the ACD variant of
Equation 10. That is, the parameter B in Equation 10 could
be set equal to zero without adversely affecting the fit to the
data. For the data obtained by Ishii (1966) for the constant
feed composition system, Equation 10 simplified to the two-
parameter expression given by Equation 14. I n most systems
no such simplifications will be found to apply, and the general
version of Equation 10 will have to be employed.
The initial rate of reaction as calculated from the derived
temperature relationships for the Types 11 and 210 catalysts
for a typical industrial composition of 8% so2, 13% 02, and
7970 iY2 exhibited parabolic relationships with temperature
for temperatures between 450" and 6OO'C. A flattening off of
the curve toward a maximum rate was exhibited by the Type
11catalyst, while an actual maximum value occurred a t 550'C
with the Type 210 catalyst. Such behavior is impossible to
model with any form of power series expression, including
Equation 11, in which the same values of the exponents are
assumed to apply a t each temperature and the specific rate
constant is assumed to follow an Arrhenius relationship. This
form of relationship yields initial rates of reaction which
increase a t an ever-increasing rate with increasing tempera-
ture. When Equation 11 was used to correlate the data for the
Types 11 and 210 catalysts, different power dependencies
applied a t each temperature and the values of the specific
rate constant, A , did not increase monotonically with tem-
perature.
The equilibrium factor included in Equation 10 was Feq.
This factor was found t o be satisfactory in the kinetic ex-
pression developed by Krichevskaya (1947) while certain SUBSCRIPTS
authors (Boreskov e t al., 1967, 1968; Eklund, 1956; Kubota c = calculated
e t al., 1959) have preferred t o use F,,1 in their kinetic ex- e = experimental
pressions. Since Equation 10 exhibits a good fit t o t h e data j = final conditions
from many sources, t h e inclusion of F,, in Equation 10 has
literature Cited
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Acknowledgment Boreskov, G. K., J . Phys. Chem. (U.S.S.R.), 19, 535 (1945).
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126-32’(1967). ”
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Duecker, W. W., West, J. R., “The Alanufacture of Sulphuric
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(Pso2;:;1:pKp) Acid,” pp 143-58, Reinhold, New York, S.Y., 1959.
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1- (P s o 2 ; ~ ~ / ~ K P ) ’
Stockholm, 1956.
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Glueck, A. R., Kenny, C. N., Chem. Eng. Scz., 23, 1257-65
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56 (1960).
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Po2,Pso2,PsoS = interfacial partial pressures of On, SOn, (1961).
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Vol 3, Chaps. 19, 21, Wiley, Kew York, X.Y., 1947.
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~ interfacial partial pressures of 0 2 and SO2 Hougen, 0. A,, Watson, K. M., Znd. Eng. Chem., 35,529-41 (1943).
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the reactor under consideration, a t m (1966).
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319-29 (1970).
catalvst)
. , I
Kiyoura, R., Sczence (Japan), 10, 126 (1940).
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r,, = average rate of reaction = - re i i a ~ 7,. 1
N ,At,*,

Kubota, H., Ishizawa, XI Shindo, AI., Sulphuric Acid (Japan),

S, = total sum of squares of experimental rates about the 12. 243-51 (19,59).
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Mars, P., llaessen, J. G. H., Proc. 3rd I n t . Congr. on Catalysis,
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1

analyses of the inlet and outlet reactor gases, liters Mars, P., van Krevelen, 11. R.,Chem. Eng. Sci., 3, Special
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100 -v I T , - re’ Mathur, G. P., Thodos, G., {bid., 21, 1191-1200 (1966).
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GREEKLETTERS
RECEIVED for review February 29, 1972
APso3 = film diffusion pressure differential of SOS,a t m ACCEPTEDJune 29, 1972

Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972 573